Process for the production of unsaturated organosilicon compounds

ABSTRACT

Process for the production of unsaturated organosilicon compounds by the reaction of chloro- and alkoxy-substituted silicon hydrides containing one Si-II bond with conjugated dienic hydrocarbons and derivatives thereof, containing at least two C C bonds. The reactants are contacted in the presence of Pd(11) compounds, such as PdCl2, PdBr2, Pd(acetylacetonate)2, compleces of general formula L1L2PdX2 , L3PdX2 , and (L4PdY)2 where L1 and L2 is a tertiary phosphine, preferably triphenylphosphine, or a nitrile, preferably benzonitrile, L3 is a ditertiary phosphine, preferably 1,2bis(triphenylphosphine)ethane, or a dinitrile, preferably Oxylylenedinitrile, L4 is a coordinated alkene or an alkenic fragment, PREFERABLY PI-ALLYL GROUP, X is chlorine or bromine atom, and Y is chlorine atom or acetoxy group. The substances formed by contacting the above defined Pd(11) compounds with organic polymers contain tert.amine, tert. phosphine, or nitrile groups, or these groups in a suitable combination, the preferred polymers being polystyrene, copolymers of styrene with divinylbenzene or with allyl chloride, poly(vinyl chloride), polymethacrylates and their copolymers.

United States Patent [191 Svoboda et al.

[ Feb. 4, 1975 PROCESS FOR THE PRODUCTION OF UNSATURATED ORGANOSILICON COMPOUNDS [73] Assignee: Ceskoslovenska Akademie ved,

Praha, Czechoslovakia [22] Filed: Dec. 1, 1972 [21] Appl. No.: 311,270

[30] Foreign Application Priority Data Dec; 10, i971 Czechoslovakia 8623-7l Dec. 16, 197i Czechoslovakia 8758-7l Mar. 2, 1972 Czechoslovakia l362-72 Mar. 29, I972 Czechoslovakia 2l02-72 [52] U.S. Cl..... 260/4482 E, 252/431, 260/448.8 R [5 l] Int. Cl. C07f 7/08 [58] Field of Search 260/4482 E, 448.8 R; 252/43l [56] References Cited UNITED STATES PATENTS 3,159,662 12/1964 Ashby 260/4482 E Primary Examiner- Paul F. Shaver [57] ABSTRACT Process for the production of unsaturated organosilicon compounds by the reaction of chloroand alkoxysubstituted silicon hydrides containing one Si-ll bond with conjugated dienic hydrocarbons and derivatives thereof, containing at least two C=C bonds. The reactants are contacted in the presence of Pd(ll) compounds, such as PdCl PdBr Pd(acetylacetonateh, compleces of general formula LUPdX L PdX and (LPdY) where L and L is a tertiary phosphine, preferably triphenylphosphine, or a nitrile, preferably benzonitrile,

L is a ditertiary phosphine, preferably l,2-bis(triphenylphosphine)ethane, or a dinitrile,

preferably O-xylylenedinitrile,

L is a coordinated alkene or an alkenic fragment, preferably pi-allyl group,

X is chlorine or bromine atom, and

Y is chlorine atom or acetoxy group.

The substances formed by contacting the above defined Pd(l l) compounds with organic polymers contain terLamine, tert. phosphine, or nitrile groups, or these groups in a suitable combination, the preferred polymers being polystyrene, copolymers of styrene with divinylbenzene or with allyl chloride, poly(vinyl chloride), polymethacrylates and their copolymers.

7 Claims, No Drawings 1 PROCESS FOR THE PRODUCTION OF UN SATURATED ORGANOSILICON COMPOUNDS The present invention relates to a process for the production of unsaturated organosilicon compounds by hydrosilylation of conjugated dienic hydrocarbons and their derivatives.

It is known in the art that the reaction of organosilicon compounds containing one Si--H bond with alkenic hydrocarbons containing two conjugated C=C bonds leads to several types of products: monosilylsubstituted alkenes (1:1 adducts), formed by the addition of one molecule of an organosilicon hydride to one molecule of a diene, further disilyl-substituted alkanes (2:1 adducts), which are the products of the addition of two molecules of the silicon hydride to one molecule of the hydrocarbon, and last, but not least, monosilylsubstituted alkadienes (X 1:2 adducts), which are the products of the reaction of one molecule of the silicon hydride with'two molecules of the diene.

Processes so far known in the art enable to prepare compounds of the first type, i.e., the 1:1 adducts, only with difficulty or in comparatively low yields, especially when chloroor alkoxy-substituted silicon hydrides are used as reactants. So, for instance, nbutenyltrichlorosilane was obtained by reacting trichlorosilane with butadiene in the presence of diacetyl peroxide as the initiator at 300C for 24 hours (.1. Am. Chem. Soc. 69,2916 (1947), US. Pat. No. 2,626,271). The additions catalysed with platinum-on-supports catalysts or with soluble platinum compounds yield as a rule a mixture of 1:1 and 2:1 adducts, with low content of the 1:1 adducts. In some cases also other side products are formed. As an example, the reaction of trichlorosilane with butadiene catalysed with 0.77 percent Pt/C and carried out at 160C over a period of 2,5 hours gave the 1:1 adduct in 40 percent yield and the 2:1 adduct in 30 percent yield (US. Pat. No. 2,637,738). Hydrosilylation of butadiene with methyldichlorosilane catalysed with the 1% Pt/C catalyst at 160C gave after 10 hours only 14 percent yield of the corresponding 1:1 adduct. The reaction was accompanied by an extensive formation of side products, the major one being the adduct of methyldichlorosilane and vinylcyclohexene. The latter compound was formed during the reaction by cyclodimerization of butadiene(1zv.Akad. Nauk SSSR, otd. khim. nauk 1957, 1206). The low selectivity is exhibited also by one of the most widely used hydrosilylation catalysts, chloroplatinic acid. The addition of methyldichlorosilane to piperylene, carried out at l120C for 5 hours, yielded the 1:1 adduct in 43 percent yield (lzv. Akad. Nauk. SSSR, itd, khim. nauk 1960, 1419). On addition of triethoxysilane to isoprene, the 1:] adduct was formed in 17 percent yield, and similar reaction of trichlorosilane with chloroprene afforded the corre sponding 1:1 adduct in only 7 percent yield (Azerb,

Khim. Zhur. 1962 (2), 9; Chem. Abstr. 59,5189

The few selective catalytic systems so far available, which were found to direct the addition of trichlorosilane to 1,3-butadiene to the nearly exclusive formation of the 1:1 adduct, are metallic palladium in the presence of an excess of a tertiary phosphine (J Chem. Soc. (D), 1971, 247) and a zero-valent palladium complex, bis(triphenylphosphine) (malei anhydride) palladium (OrganometaL- Chem. Synth. 1,193 (1971) These catalysts, although highly selective, suffer from some disadvantages. In the first case, a high molar excess ofa tertiary phosphine, relative to the metal, is unavoidable (e.g., 10:1), in the other one the catalyst is prepared by multi-step process, the last being the reaction of the in the air extremely unstable tetrakis (triphenylphosphine) palladium with maleic anhydride (J. Chem. Soc. Japan, Pure Chem. Sect. 83,454 (1968) The object of the present invention is to provide a process for the production of unsaturated organosilicon compounds which makes it possible to carry out the addition reaction of silicon hydrides to conjugated dienic hydrocarbons and their derivatives under mild conditions with good yields of the 1:1 adducts. According to the invention the reaction of silicon hydrides of general formulae where R is methyl or ethyl group and n equals to zero or to one, and

L'L PdX L PdX and (LPdY) where' L and L is a tertiary phosphine, preferably triphenylphosphine, or a nitrile, preferably benzonitrile,

L is a ditertiary phosphine, preferably 1,2-bis(- triphenyl-phosphine) ethane, or an organic dinitrile, preferably o-xylylene-dinitrile,

L is a coordinated alkene or alenic fragment, preferably pi-allyl group,

X is chlorine or bromine atom, and

Y is chlorine atom or acetoxy group, and also the compounds formed by contacting substances of the above defined types with organic polymers containing tert. amine, tert. phosphine or nitrile groups, or these groups in a suitable combination, the preferred polymers being polystyrene, copolymers of styrene with divinylbenzene or with allyl chloride, poly- (vinyl chloride), polymethacrylates and their copolymers.

The reaction can be effected both in the absence and in the presence of a solvent, under the pressure of the vapours of reaction components at the reaction temperature or under an elevated pressure, adjusted by an inert gas, preferably nitrogen or argon. The catalysts which contain the transition metal bonded to the organic groups of polymeric compounds make it possible to perform the reaction also in the gas phase. As a solvent, any substance which does not react with the reactants, dissolves the catalyst and the reacting compounds can be used. Such solvents are, for instance, ethers, such as tetrahydrofurane, or aromatic hydrocarbons such as benzene, toluene, a xylene, etc. The choice of the reaction temperature is influenced above all by the reactivity of the starting compounds. With chloro-substituted silicon hydrides, the reaction with butadiene or with isoprene can be carried out already at temperatures from 15 to +20C. With majority of geous to work at temperatures 20- l30C.

Although relative amounts of a silicon hydride and a dienic hydrocarbons are determined by stoichiometry EXAMPLE 2 Example I was repeated with the exception that the reaction components were added in the order: the catalyst, the butadiene, and the chlorosilane. Distillation of the reaction (the hydride to the diene molar ratio 5 afforded the M adduct In 915 percent yield. lzl the reaction can be carried out also with'non-stoichiometric ratios of the reaction components. So. for I EXAMPLE 3 version of l'l adduct and enables obtain the desired In L parts g ggg i f pans g g uta ien arts enzene was eate in an yields in a shorter time. The amount of catalysts can aumclav: tz sooc s a period of 2 hours The yield vary within wide limits. The palladium catalysts deof the Corresponding adduct was 83 p'ercem scribed in this invention are effective already in the amounts of about 1 mol palladium per 1X10 mol of a EXAMPLE 4 dienic hydrocarbon; the maximum of the catalyst is dic- A mixture of 142g of I 3 butadI-ene 5 g of toluene 31 .11 tliiliiiiifi?figil'ihl iiiii'i$ZJFSZSQ g d si: "i "il' I I I )palladiumdichloride, coole to l was a lowe to EL"iil$l i Z5501:lift; $2li%6"$i%833$'1 Si warm "v the temperature whi'e a dienic hydrocarbon The reaction course is not furofmghlomsllime was aqded i after the exotherl Ih l ff d b the metallic alladium mic reaction subsided (during which the temperature f er z gs z f f z most caseq thgreaction of the reaction mixture rose to 10C) an additional cz u i s e does nit de end also on the order in which indi (201 g) trichlofosilane was .pomqn'wise added while vidual components are added to the reaction mixture. externally Cooling the rezicnon .mlxwre.such the With alkenic palladium complexes it is however advan- 3: 8 g gfi zg gsy mlxtsuzre g r g f fi tageous to use them, or the silicon hydride, as the last I I component In the preparation of tha reaction mixtureI butenyltrichlorosllane (the (318 to trans ratio 9.1

The alkenylsilanes prepared according to this inven- EXAMPLE 5 tion contain reactive groups and can be thus employed I I I I as starting compounds in preparing other organosilicon I 'l l repeated except that. blslpl derivatives They can be further used for hydrofobisaany]ldlpanadlgnldlchlond? mg) used "l place tion of 'g materials or III p g agents for of b1s(benzomtnle)palladlumdichloride. The yleld of cross-linking of inorganic materials with organic polythe m adduct was 76 percent mers. EXAMPLE 6 The following examples are illustrative ofthe practise 35 A mixture 0H6 g ofliquid I 3 bumdiene 68 g of i j g 2353:? s thyldichlorosilane, and 28 mg of bis(benzonitrile)pallan 655 o erwlse p y diumdichloride was reacted as described in Example 4. yielding 62 percent 2-butanylmethyldichlorosilane.

EXAMPLE 1 EXAMPLE 7 Into a cooled pressure vessel were introduced 1 part A lass ampoule was charged with 1 art ofa catag P of bis(benzonitrile) palladiumdichloride, 67 parts of lyst, and appropriate amounts ofa silicon hydride and trichlorosilane, and 32.5 arts ofli uid 1,3-butadiene. a dienic h drocarbon were added. After sealing, the

P 1 y I The reaction vessel was closed and then heated at 80C contents were allowed to stand at ambient temperature over a period of 2 hours. Distillation afforded the 1:1 or heated to the desired temperature for a desired time. adduct, cis-2-butenyltrichlorosilane, in 87 percent Conversions ofstarting chloro-substituted silanes to 1:] yield. adducts, determined by g.l.c., are given in Table I.

TABLE I (EXAMPLE 7) Dicnc Silicon hydride Reaction Reaction Conversion to 1:] (w. parts) (w.parts) Catalyst temp..C time. h adducts, in '71 l,3-butadiene(32.5) trichlorosilanc(67) /(pi-allyl)PdCl/, 80 2 9l l.3-butadiene(32.5) trichlorosilanc(67) (C,,H .,CN) PdCl 100 2 92 lt3-butadiene( 37) trichlorosilane( 62) /(C H ',);;P/-,PdBr- 80 2 l,3-butadicnc( 32.5) trichlorosilanc( 7) /0-C H myyg/z g 0 Z 92 l.3-hutadiene( 32.5) methyldichlorosilane( 63) /(pi-allyl )PdCl/ 2 67 l.3-hutadicnc( 37) trichlorosilanc(67) /(pi-allyl )PdCl/ 23 30 67 l.3-hutadienc( 35) cthyldichlorosilanc(65) pi-allyl )PdCl/ X0 5 36 l.3hutadicnc(32.5) trichlorosilanet67) 2 120 3 78 isoprene( 42) trichlorosilanc( 72) (C H CN )zPdClg 80 2 87 isoprcnc( 39) methyldichlorosilanfl 65) pi-allyl )PdCl/ 80 2 64 2.3-dimcthyH .3'hutadicnc( 35) mcthyldichlorosilanfl 62) (C H -,CN )gPdCl-z 80 2 27 pipcrylcnc(36) trichlorosilanc(69) /(pi-:|llyl)PdCl/ 90 4 72 Cllloroprcnc(4l mcthyldichlorosilanc( 70) /(C. H ,);;P/ Pdt'.l 90 7 37 EXAMPLE 8 A mixture of parts of a macroreticular styrenedivinylbenzene copolymer containing 5.l percent P in the form of the --CH P(C H groups, 5 parts of palladium(l l) chloride, and I parts of ethanol was heated to ll0 C for 6 hours. After separation of the polymer. followed by its washing with three IOO-ml. portions of ethanol and its drying, the catalyst contained 10.9% Pd.

EXAMPLE 9 A macroreticular styrene-divinylbenzene copolymer containing on its surface -CH CN groups was allowed to stand with 8 percent aqueous palladium chloride solution for 20 hours. Five parts ofthe solution per 1 part of the polymer were used. After filtration and drying, the catalyst contained 3.0% Pd.

of 6 hours. After separation. washing with 30 parts of chloroform and 15 parts of ethanol. and drying. the catalyst contained 1.82% Pd. 1

EXAMPLE 14 TABLE I] (EXAMPLE l5) Dicne Silicon hydride Catalyst Reaction Reaction Conversion to (w. parts) (w. parts) from Example temp.,C time, h l:l adduets l,3-butadiene(72) lrichlorosilanel 78) 8 90 3 73 l.3-hutadiene(52) lrichlorosilanet48) 9 23 24 85 l,3-hutadienet 52) trichlorosilanet 72) 10 I00 2 76 l.3-butadienet(r2) triehlorosiltmdfi'll 12 80 2 56 l.3-hutadienet47l ethyldiehlorosilanct51 l I4 80 2 88 isoprenetfill v trichlorosilanet47) ll 80 2 47 isoprenet 5?.) trichlorosilunet bl l3 1 l0 3 86 isoprenet 53) methyltliehlorosilanel 8 80 2 )l isoprenet 56) ethyldichlorosilanet 49) 8 80 2 87 2.3-dimethyl-l .3-

-hutadiene( 55) trichlorosilanet 52) 9 90 3 43 pieprylenet 52) trichlorosilunet 55) 13 80 3 83 chloroprene(6l ethyldichlorosilanet 67] 8 H0 5 32 EXAMPLE l0 EXAMPLE 16 A macroreticular copolymer of styrene with divinylbenzene containing surface -CH N(CH groups was saturated in the column by washing with 1 percentaqueous palladium(l l) chloride solution. Forty parts of the solution per 1 part of the polymer were used. After drying. the catalyst contained 14.2% Pd.

EXAMPLE ll A macroreticular copolymer of 2- dimethylaminoethyl methacrylate with ethylenedimethacrylate Was washed in the column with l percent aqueous solution of palladium( l l) chloride. The solution was used in the weight ratio with respect to the polymer. After drying, the catalyst contained 18.4% Pd.

EXAMPLE 12 A macroreticular copolymer of 2-cyanoethyl methacrylate with ethylene-dimethacrylate was washed in the column with 5 percent aqueous palladium( l l chloride solution. The weight ratio of the solution to the polymer was 10: l After drying, the catalyst contained 0.5% Pd.

EXAMPLE l3 A mixture of 12 parts of a copolymer ofallylchloride with divinylbenzene, containing surface CH P(C H,-,) groups, 4.5 parts of bist triphenylphosphine)palladiumdichloride. 35 parts of chloroform, and 15 parts of ethanol was heated at 60C for a period EXAMPLE l7 A mixture of l,3-butadiene and trichlorosilane vapours was passed over 6 parts of the catalyst from Example 9 at 100C in the flow rate 0.14 mol per h CH., and 0.06 mol per h HSiCl Chromatographic analysis showed 80 percent conversion of the silicon hydride in n-butenyltrichlorosilane.

EXAMPLE 18 A mixture of l part of the catalyst from Example 10, parts of triethoxysilane, and 40 parts of liquid L3- butadiene was heated under the vapour pressure of the reactants to 85C for 2 hours. n-Butanyltriethoxysilane was obtained in 52 percent yield.

EXAMPLE 1) A cooled reaction vessel was charged with 1 part of bis-(pi-allyl)-dipalladiumdichloride. 65 parts of triethoxysilane. and 35 parts of liquid 1.3-butadiene. After sealing, the reaction mixture was maintained at C for 2 hours. After this period of time the butadiene reacted from 68 percent to give a mixture of the l:l adduct, n-butenyltriethoxysilane, and the 1:2 adduct, ana octadienyltri-ethoxysilane, in the ratio 2:].

What we claim is:

1. A process for the production of unsaturated organosilicon compounds which comprises contacting a silicon compound containing one hydrogen atom attached to silicon per molecule, with a dienic hydrocarbon containing conjugated Ci: double bonds and having from four to eight carbon atoms per molecule in the presence of a palladium complex selected from the group consisting of L.,PdX- L 'PdX UPdXCl and (1r--C;,H,-,)PdCl/ where L is a member selected from the group consisting of tertiary phosphines having at least one phenyl group attached to phosphorus per molecule, X is a member selected from the group consisting of halogens, L is benzonitrile, L" is l,2-bis(triphenylphosphine) ethane or l,2-bis(cyanomethyl)benzene, and where rrC H is a pi-allyl group.

2. A process for the production of unsaturated organosilicon compounds according to claim 1, wherein the palladium complex has the formula:

L PdX 3. A process for the production of unsaturated organosilicon compounds according to claim 1, wherein the palladium complex has the formula:

LZ PdX 4. A process for the production of unsaturated organosilicon compounds according to claim I. wherein the palladium complex has the formula:

5. A process for the production of unsaturated organosilicon compounds according to claim 1, wherein the palladium complex has the formula:

6. A process for the production of unsaturated organosilicon compounds according to claim 1, wherein the organosilicon compound has the formula:

z slH where R is a member selected from the class consisting of methyl, ethyl, and propyl radicals and with 1,3-

butadiene. 

1. A PROCESS FOR THE PRODUCTION OF UNSATURATED ORGANOSILICON COMPOUNDS WHICH COMPRISES CONTACTING A SILICON COMPOUND CONTAINING ONE HYDROGEN ATOM ATTACHED TO SILICON PER MOLECULE, WITH A DIENIC HYDROCARBON CONTAINING CONJUGATED C=C DOUBLE BONDS AND HAVING FROM FOUR TO EIGHT CARBON ATOMS PER MOLECULE IN THE PRESENCE OF A PALLADIUM COMPLEX SELECTED FROM THE GROUP CONSISTING OF L2PDX2, L21PDX2, L3PDXCL2, AND ($-C3H5)PDCL/2 WHERE L IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF TERTIARY PHOSPHINES HAVING AT LEAST ONE PHENYL GROUP ATTACHED TO PHOSPHINES PER MOLECULE, X IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF HALOGENS, L1 IS BENZONITRILE, L3 IS 1,2BIS(TRIPHENYLPHOSPHINE) ETHANE OR 1,2BIS(CYANOMETHYL)BENZENE, AND WHERE $-C3H5 IS A PI-ALLYL GROUP.
 2. A process for the production of unsaturated organosilicon compounds according to claim 1, wherein the palladium complex has the formula: L2PdX2.
 3. A process for the production of unsaturated organosilicon compounds according to claim 1, wherein the palladium complex has the formula: L21PdX2.
 4. A process for the production of unsaturated organosilicon compounds according to claim 1, wherein the palladium complex has the formula: L3PdXCl2.
 5. A process for the production of unsaturated organosilicon compounds according to claim 1, wherein the palladium complex has the formula: ( pi -C3H5)PdCl/2.
 6. A process for the production of unsaturated organosilicon compounds according to claim 1, wherein the organosilicon compound has the formula: RnSiHCl3 n where R is methyl or ethyl radical and n is equal to zero or to one and is contacted with a conjugated diene selected from the class consisting of 1,3-butadiene, isoprene, piperylene, chloroprene, and 2,3-dimethyl-1,3-butadiene.
 7. A process for the production of unsaturated organosilicon compounds according to claim 1, wherein the organosilicon compound has the formula: (RO) 3SiH where R is a member selected from the class consisting of methyl, ethyl, and propyl radicals and with 1,3-butadiene. 